CN117964654A - Synthesis method of arginate-ammonium phosphonate - Google Patents
Synthesis method of arginate-ammonium phosphonate Download PDFInfo
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- CN117964654A CN117964654A CN202410110397.3A CN202410110397A CN117964654A CN 117964654 A CN117964654 A CN 117964654A CN 202410110397 A CN202410110397 A CN 202410110397A CN 117964654 A CN117964654 A CN 117964654A
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- ammonium
- hydrochloride
- reaction
- glufosinate
- homoserine lactone
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- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims abstract description 18
- 238000001308 synthesis method Methods 0.000 title claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 41
- XBKCXPRYTLOQKS-DFWYDOINSA-N [(3s)-2-oxooxolan-3-yl]azanium;chloride Chemical compound Cl.N[C@H]1CCOC1=O XBKCXPRYTLOQKS-DFWYDOINSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 46
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 4
- RDVLKFWQJDSWBB-UHFFFAOYSA-N Cl.OP(O)=O Chemical compound Cl.OP(O)=O RDVLKFWQJDSWBB-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- -1 methylphosphonous acid di-tert-butyl ester Chemical compound 0.000 claims description 3
- KBFVVXQEHYTXRK-VKHMYHEASA-N (2S)-2-(chloroamino)-4-hydroxybutanoic acid Chemical compound ClN[C@@H](CCO)C(=O)O KBFVVXQEHYTXRK-VKHMYHEASA-N 0.000 claims description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- PMVVRSKJCGEFIY-UHFFFAOYSA-N methylphosphonous acid Chemical compound CP(O)O PMVVRSKJCGEFIY-UHFFFAOYSA-N 0.000 claims description 2
- ZEOQPNRYUCROGZ-UHFFFAOYSA-N n,n-dibutylbutan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH+](CCCC)CCCC ZEOQPNRYUCROGZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- KLBOFRLEHJAXIU-UHFFFAOYSA-N tributylazanium;chloride Chemical compound Cl.CCCCN(CCCC)CCCC KLBOFRLEHJAXIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000005051 trimethylchlorosilane Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- JZVMQGJXQXMDHF-UHFFFAOYSA-N dibutoxy(methyl)phosphane Chemical compound CCCCOP(C)OCCCC JZVMQGJXQXMDHF-UHFFFAOYSA-N 0.000 claims 1
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 claims 1
- ZXMSTCRBSAVFDO-UHFFFAOYSA-N dimethoxy(methyl)phosphane Chemical compound COP(C)OC ZXMSTCRBSAVFDO-UHFFFAOYSA-N 0.000 claims 1
- MJKANHGOJWIKJW-UHFFFAOYSA-N methyl(diphenoxy)phosphane Chemical compound C=1C=CC=CC=1OP(C)OC1=CC=CC=C1 MJKANHGOJWIKJW-UHFFFAOYSA-N 0.000 claims 1
- NCOCMUZFTUBKPR-UHFFFAOYSA-N methyl(dipropoxy)phosphane Chemical compound CCCOP(C)OCCC NCOCMUZFTUBKPR-UHFFFAOYSA-N 0.000 claims 1
- IIXDCLXRMJQEAM-UHFFFAOYSA-N methyl-di(propan-2-yloxy)phosphane Chemical compound CC(C)OP(C)OC(C)C IIXDCLXRMJQEAM-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000005580 one pot reaction Methods 0.000 abstract description 4
- QJPWUUJVYOJNMH-VKHMYHEASA-N L-homoserine lactone Chemical compound N[C@H]1CCOC1=O QJPWUUJVYOJNMH-VKHMYHEASA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- ZBMRKNMTMPPMMK-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid;azane Chemical compound [NH4+].CP(O)(=O)CCC(N)C([O-])=O ZBMRKNMTMPPMMK-UHFFFAOYSA-N 0.000 abstract 2
- 239000005561 Glufosinate Substances 0.000 description 12
- 238000001514 detection method Methods 0.000 description 10
- 238000005070 sampling Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- IAJOBQBIJHVGMQ-BYPYZUCNSA-N glufosinate-P Chemical compound CP(O)(=O)CC[C@H](N)C(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UTZAXPKCGJZGLB-UHFFFAOYSA-N diethyl methyl phosphite Chemical compound CCOP(OC)OCC UTZAXPKCGJZGLB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009333 weeding Methods 0.000 description 3
- NAAGLMQVFHHOHD-UHFFFAOYSA-N C(CC)OP(OCCC)(O)C Chemical compound C(CC)OP(OCCC)(O)C NAAGLMQVFHHOHD-UHFFFAOYSA-N 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- IAJOBQBIJHVGMQ-SCSAIBSYSA-N (2R)-glufosinate Chemical compound C[P@@](O)(=O)CC[C@@H](N)C(O)=O IAJOBQBIJHVGMQ-SCSAIBSYSA-N 0.000 description 1
- SNRMSFWQDNTNHM-UHFFFAOYSA-N C(C)(C)OP(OC(C)C)(O)C Chemical compound C(C)(C)OP(OC(C)C)(O)C SNRMSFWQDNTNHM-UHFFFAOYSA-N 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- BULLZDQQGFJWHZ-UHFFFAOYSA-N dibutyl methyl phosphite Chemical compound CCCCOP(OC)OCCCC BULLZDQQGFJWHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 102000005396 glutamine synthetase Human genes 0.000 description 1
- 108020002326 glutamine synthetase Proteins 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- NYCZNDFWFCCTPA-UHFFFAOYSA-N methyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC)OC1=CC=CC=C1 NYCZNDFWFCCTPA-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Abstract
The invention belongs to the technical field of synthesis of organic compounds, and particularly relates to a synthesis method of glufosinate-ammonium hydrochloride. According to the invention, homoserine lactone hydrochloride is used as an initiator to sequentially undergo esterification reaction and substitution reaction under the action of a catalyst, so that the arginate-ammonium phosphonate is obtained, and then the arginate-ammonium phosphonate is hydrolyzed to obtain a final product. The method for preparing the glufosinate-ammonium hydrochloride provided by the invention uses the L-homoserine lactone hydrochloride as a starting material, and synthesizes the target compound through a one-pot method, so that the synthetic route is shortened, the three-waste yield is reduced, and the cost is reduced. The raw materials required by synthesis are easy to obtain, the cost is controllable, the synthesis route is simple, the post-treatment is convenient, the yield is considerable, and the method has high industrial application value.
Description
Technical Field
The invention belongs to the technical field of synthesis of organic compounds, and particularly relates to a synthesis method of glufosinate-ammonium hydrochloride.
Background
Glufosinate is an organophosphorus biocidal herbicide developed by helter in the 80 s of the 20 th century, and the mechanism of action is to inhibit glutamine synthetase in plants, resulting in disturbance of nitrogen metabolism in plants, inhibiting photosynthesis in plants, and causing death of plants. The glufosinate has the remarkable characteristics of high weeding activity, low phytotoxicity, low residue, wide weeding spectrum, high safety and the like, and is one of main biocidal herbicide in the market at present.
The glufosinate has two configurations of D-glufosinate and L-glufosinate, and researches show that only L-glufosinate has herbicidal activity. Most of the commercial glufosinate is raceme and racemic glufosinate compound preparation, and the required dosage of the L-glufosinate is only half of the dosage of the racemic glufosinate under the condition of achieving the same weeding effect. Therefore, the glufosinate-ammonium has higher economical efficiency and application prospect. Although the technology of DL-glufosinate-ammonium is very mature, the research of L-glufosinate-ammonium still stays in the laboratory stage, so that the research and development of the production technology of L-glufosinate-ammonium has important significance.
The synthesis method of glufosinate mainly comprises Albuzoff synthesis method, high-pressure catalytic synthesis method, low-temperature directional synthesis method, geburill-diethyl malonate synthesis method, sizogram-Zells base synthesis method, chiral synthesis method and the like. However, the existing synthetic route has the problems of higher cost, harsh reaction conditions, complex steps, more waste materials, and the like, and limits industrial production. The synthesis process of glufosinate is improved, and a new synthesis route is explored.
The invention utilizes homoserine lactone hydrochloride as a starting material, combines an Abuzoff synthesis method with a one-pot method, and provides a simple synthesis method for preparing the glufosinate-ammonium and the hydrochloride thereof, which has low cost, high yield and less three wastes.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a synthesis method of glufosinate-ammonium hydrochloride. The invention synthesizes the target compound by using L-homoserine lactone hydrochloride as a starting material through a one-pot method, shortens the synthetic route, reduces the three-waste output and reduces the cost. The raw materials required by synthesis are easy to obtain, the cost is controllable, the synthesis route is simple, the post-treatment is convenient, the yield is considerable, and the method has high industrial application value.
The aim and the technical problems of the invention are realized by adopting the following technical proposal.
The invention provides a synthesis method of glufosinate-ammonium hydrochloride, which comprises the following steps:
(1) Synthesizing the arginate-ammonium phosphonate (III) by taking L-homoserine lactone hydrochloride (II) as a raw material:
adding a solvent, alcohol and a catalyst into L-homoserine lactone hydrochloride, heating to 120-140 ℃ for reflux reaction for 12-18h, and cooling to room temperature after the reaction is completed to obtain an intermediate chlorohomoserine ester hydrochloride; then adding methyl phosphite active ester and a phase transfer catalyst into the reaction solution under inert atmosphere, heating to 120-140 ℃ for reflux reaction for 12-18h, and obtaining a arginate-ammonium phosphonate reaction solution after the reaction is completed;
The reaction formula is as follows:
wherein R1 represents methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl;
R2 represents methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl and phenyl;
(2) Preparation of glufosinate-ammonium hydrochloride (I) by using glufosinate-ammonium (III) as a raw material:
Adding concentrated hydrochloric acid into the obtained arginate-ammonium phosphonate reaction solution, heating to 80-100 ℃ for reaction for 6-12h, cooling to room temperature after the reaction is completed, standing for separating liquid, distilling a lower aqueous phase under reduced pressure to remove water, crystallizing, and performing suction filtration to obtain arginate-ammonium phosphonate hydrochloride;
The reaction formula is as follows:
Preferably, the catalyst in the step (1) is selected from one or a mixture of several of zinc chloride, aluminum chloride, ferrous chloride, ferric chloride, phosphorus trichloride, phosphorus pentachloride, trimethylchlorosilane, p-toluenesulfonic acid, p-toluenesulfonyl chloride and liquid bromine.
Preferably, the alcohol in the step (1) is selected from one or a mixture of several of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol; the molar equivalent of the alcohol and L-homoserine lactone hydrochloride is 1.5-3.0.
Preferably, the solvent in the step (1) is selected from one or a mixture of several of toluene, chlorobenzene, xylene, trimethylbenzene, N-dimethylformamide and N-methylpyrrolidone; the volume ratio of the solvent to the L-homoserine lactone hydrochloride is 2V-5V.
Preferably, the methylphosphonous acid active ester in the step (1) is one or a mixture of several of methyl dimethyl phosphite, diethyl methylphosphite, dipropyl methylphosphite, diisopropyl methylphosphite, dibutyl methylphosphite, diphenyl methylphosphite and di-tert-butyl methylphosphite; the molar equivalent ratio of the methylphosphite active ester to the L-homoserine lactone hydrochloride is 1.2-1.8.
Preferably, the phase transfer catalyst in the step (1) is selected from one or a mixture of more of tri-n-butyl ammonium chloride, tri-n-butyl ammonium bromide, benzyl triethyl ammonium chloride, tetrabutylammonium bisulfate, cetyl trimethyl ammonium bromide and 18-crown-6; the molar equivalent ratio of the catalyst to the L-homoserine lactone hydrochloride is 0.001-0.1.
Preferably, the hydrochloric acid concentration in step (2) is 10-30%.
Preferably, the molar equivalent ratio of hydrochloric acid to L-homoserine lactone hydrochloride in step (2) is 3-10.
Preferably, the solvent for crystallization in the step (2) is selected from one or a mixture of several of methanol, ethanol, propanol, isopropanol, diethyl ether and methyl tertiary butyl ether.
Preferably, the crystallization conditions in step (2) are: the temperature is 5-15 ℃, and the crystallization time is 12-24 hours.
By means of the technical scheme, the invention has at least the following advantages:
(1) According to the invention, homoserine lactone hydrochloride is used as an initiator to sequentially undergo esterification reaction and substitution reaction under the action of a catalyst, so that the arginate-ammonium phosphonate is obtained, and then the arginate-ammonium phosphonate is hydrolyzed to obtain a final product.
(2) The method is suitable for preparing the L-glufosinate-ammonium, shortens the synthetic route and reduces the material cost and the production cost by a one-pot method.
(3) The raw materials used in the invention are easy to obtain and cheap, the reaction time is short, the production period can be obviously shortened, and the energy consumption can be reduced.
(4) The post-treatment process of the invention is simple and only comprises three processes of liquid separation, desolventizing and crystallizing.
(5) The preparation method of the invention has wide application range, can be used for synthesizing similar compounds, and has great industrialization and commercialization values.
(6) The method for preparing the glufosinate-ammonium hydrochloride has the advantages of simple route and easy synthesis, and the used solvent can be recycled for secondary use, so that the generation of three wastes is reduced, and the method is energy-saving and environment-friendly.
The foregoing description is only an overview of the present invention, and is intended to provide a more thorough understanding of the present invention, and is to be accorded the full scope of the present invention.
Drawings
FIG. 1 is a chemical content detection chart of L-glufosinate prepared in example 1 according to the invention;
FIG. 2 is a graph showing the chemical content detection of arginate-ammonium phosphonate prepared according to example 1 of the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement of the purposes and the effects of the present invention easy to understand, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The structural formula of the arginate-ammonium phosphonate is shown as (I):
The glufosinate hydrochloride with the structure of the formula (I) according to the invention has the following preparation chemical reaction formula:
(1)
(2)
Example 1:
step one, synthesizing the arginate-ammonium phosphonate (III) by taking L-homoserine lactone hydrochloride (II) as a raw material, wherein the specific process is as follows:
L-homoserine lactone hydrochloride (sold by Nanjing Shengde biological technology research institute Co., ltd.) is used as a raw material, 27.4mL of chlorobenzene, 9.2g of ethanol and 0.01g of anhydrous aluminum chloride are added into 13.7g L-homoserine lactone hydrochloride, heating reflux is carried out for 12 hours at 135 ℃, sampling detection is carried out, after the reaction is completed, the temperature is reduced to room temperature, under the protection of nitrogen, 17.4g of diethyl methylphosphite is added into the reaction liquid, heating reflux reaction is carried out for 18 hours at 135 ℃, sampling detection is carried out, after the reaction is completed, cooling is carried out to room temperature, and the refined glufosinate reaction liquid is obtained for standby.
Step two, preparing the glufosinate-ammonium hydrochloride (I) by taking the glufosinate-ammonium (III) as a raw material, wherein the specific process is as follows:
Directly adding 68.5mL of 31% concentrated hydrochloric acid into the reaction solution of the glufosinate-ammonium obtained in the step one, heating to 100 ℃ for reaction for 8 hours, sampling and detecting, cooling to room temperature after the reaction is completed, standing for separating liquid, distilling the lower aqueous phase under reduced pressure to remove water, adding 72.5g of isopropanol into the reaction solution, uniformly stirring, crystallizing at 10 ℃ for 12 hours, and suction-filtering to obtain 15.40g (0.0851 mol) of glufosinate-ammonium, wherein the yield is 85%, and the L-type glufosinate-ammonium accounts for 95.2%.
FIG. 1 is a chemical content detection chart of L-glufosinate prepared in example 1 of the present invention; the peak with a retention time of 5.760min in the figure represents L-glufosinate, the content is 97.3%, and the rest is impurity peak; FIG. 2 is a graph showing the chemical content detection of the glufosinate-ammonium hydrochloride prepared in example 1 of the present invention; the peak with the retention time 8.869min in the figure represents the arginate-ammonium-phosphonium hydrochloride, the content of the arginate-ammonium-phosphonium hydrochloride is calculated to be 95.2% by an external standard method, the peak is 11.5min and 12.3min as characteristic peaks of the derivatization agent, and the rest is impurity peaks.
Example 2
Step one, synthesizing the arginate-ammonium phosphonate (III) by taking L-homoserine lactone hydrochloride (II) as a raw material, wherein the specific process is as follows:
L-homoserine lactone hydrochloride (sold by Nanjing Shengde biological technology research institute Co., ltd.) is used as a raw material, 27.4mL of chlorobenzene, 9.2g of isopropanol and 0.01g of anhydrous ferric chloride are added into 13.7g L-homoserine lactone hydrochloride, heating reflux is carried out for 12 hours at 140 ℃, sampling detection is carried out, cooling to room temperature after the reaction is completed, 18.9g of dipropyl methylphosphite is added into the reaction liquid under the protection of nitrogen, heating reflux reaction is carried out for 18 hours at 140 ℃, sampling detection is carried out, cooling to room temperature after the reaction is completed, and the refined glufosinate reaction liquid is obtained for standby.
Step two, preparing the glufosinate-ammonium hydrochloride (I) by taking the glufosinate-ammonium (III) as a raw material, wherein the specific process is as follows:
Directly adding 68.5mL of 31% concentrated hydrochloric acid into the reaction solution of the glufosinate-ammonium obtained in the step one, heating to 100 ℃ for reaction for 8 hours, sampling and detecting, cooling to room temperature after the reaction is completed, standing for separating liquid, distilling the lower aqueous phase under reduced pressure to remove water, adding 72.5g of isopropanol into the reaction solution, stirring uniformly, crystallizing at 0 ℃ for 24 hours, and suction-filtering to obtain 14.1g (0.064 mol) of glufosinate-ammonium hydrochloride, wherein the yield is 78%, and the L-type glufosinate-ammonium accounts for 93.8%.
Example 3:
step one, synthesizing the arginate-ammonium phosphonate (III) by taking L-homoserine lactone hydrochloride (II) as a raw material, wherein the specific process is as follows:
l-homoserine lactone hydrochloride (sold by Nanjing Shengde biological technology research institute Co., ltd.) is used as a raw material, 27.4mL of chlorobenzene, 9.2g of methanol and 0.01g of anhydrous p-toluenesulfonic acid are added into 13.7g L-homoserine lactone hydrochloride, the mixture is heated and stirred at 120 ℃ for reaction for 18 hours, sampling detection is carried out, the reaction is cooled to room temperature after the reaction is completed, 17.4g of diethyl methylphosphite is added into the reaction liquid under the protection of nitrogen, the reaction liquid is heated and refluxed at 135 ℃ for 18 hours, sampling detection is carried out, and the reaction liquid is cooled to room temperature after the reaction is completed, so that the refined glufosinate reaction liquid is obtained for standby.
Step two, preparing the glufosinate-ammonium hydrochloride (I) by taking the glufosinate-ammonium (III) as a raw material, wherein the specific process is as follows:
Directly adding 68.5mL of 36% concentrated hydrochloric acid into the reaction solution of the arginate-ammonium phosphonate obtained in the step one, heating to 100 ℃ for reaction for 8 hours, sampling and detecting, cooling to room temperature after the reaction is completed, standing for separating liquid, decompressing and distilling a lower water phase to remove water, adding 72.5g of isopropanol into the reaction solution, uniformly stirring, crystallizing at 0 ℃ for 24 hours, and suction-filtering to obtain 14.5g (0.080 mol) of arginate-ammonium phosphonate hydrochloride, wherein the yield is 80%, and the L-type arginate-ammonium phosphonate hydrochloride accounts for 96.3%.
While the invention has been described with respect to preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and that any such changes and modifications as described in the above embodiments are intended to be within the scope of the invention.
Claims (10)
1. The synthesis method of the glufosinate-ammonium hydrochloride is characterized by comprising the following steps of:
(1) Synthesizing the arginate-ammonium phosphonate (III) by taking L-homoserine lactone hydrochloride (II) as a raw material:
adding a solvent, alcohol and a catalyst into L-homoserine lactone hydrochloride, heating to 120-140 ℃ for reflux reaction for 12-18h, and cooling to room temperature after the reaction is completed to obtain an intermediate chlorohomoserine ester hydrochloride; then adding methyl phosphite active ester and a phase transfer catalyst into the reaction solution under inert atmosphere, heating to 120-140 ℃ for reflux reaction for 12-18h, and obtaining a arginate-ammonium phosphonate reaction solution after the reaction is completed;
The reaction formula is as follows:
wherein R1 represents methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl;
R2 represents methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl and phenyl;
(2) Preparation of glufosinate-ammonium hydrochloride (I) by using glufosinate-ammonium (III) as a raw material:
Adding concentrated hydrochloric acid into the obtained arginate-ammonium phosphonate reaction solution, heating to 80-100 ℃ for reaction for 6-12h, cooling to room temperature after the reaction is completed, standing for separating liquid, distilling a lower aqueous phase under reduced pressure to remove water, crystallizing, and performing suction filtration to obtain arginate-ammonium phosphonate hydrochloride;
The reaction formula is as follows:
2. The preparation method according to claim 1, wherein the catalyst in the step (1) is selected from one or more of zinc chloride, aluminum chloride, ferrous chloride, ferric chloride, phosphorus trichloride, phosphorus pentachloride, trimethylchlorosilane, p-toluenesulfonic acid, p-toluenesulfonyl chloride and liquid bromine.
3. The preparation method according to claim 1, wherein the alcohol in the step (1) is selected from one or more of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and tert-butanol; the molar equivalent of the alcohol and L-homoserine lactone hydrochloride is 1.5-3.0.
4. The preparation method according to claim 1, wherein the solvent in the step (1) is selected from one or more of toluene, chlorobenzene, xylene, trimethylbenzene, N-dimethylformamide, and N-methylpyrrolidone; the volume ratio of the solvent to the L-homoserine lactone hydrochloride is 2V-5V.
5. The preparation method according to claim 1, wherein the methylphosphonous acid active ester in the step (1) is one or a mixture of several of methylphosphonous acid dimethyl ester, methylphosphonous acid diethyl ester, methylphosphonous acid dipropyl ester, methylphosphonous acid diisopropyl ester, methylphosphonous acid dibutyl ester, methylphosphonous acid diphenyl ester and methylphosphonous acid di-tert-butyl ester; the molar equivalent ratio of the methylphosphite active ester to the L-homoserine lactone hydrochloride is 1.2-1.8.
6. The preparation method according to claim 1, wherein the phase transfer catalyst in the step (1) is selected from one or a mixture of several of tri-n-butyl ammonium chloride, tri-n-butyl ammonium bromide, benzyl triethyl ammonium chloride, tetrabutylammonium bisulfate, cetyl trimethyl ammonium bromide, and 18-crown-6; the molar equivalent ratio of the catalyst to the L-homoserine lactone hydrochloride is 0.001-0.1.
7. The process according to claim 1, wherein the hydrochloric acid concentration in step (2) is 10 to 30%.
8. The process according to claim 1, wherein the molar equivalent ratio of hydrochloric acid to L-homoserine lactone hydrochloride in step (2) is 3-10.
9. The method according to claim 1, wherein the solvent for crystallization in the step (2) is selected from one or more of methanol, ethanol, propanol, isopropanol, diethyl ether, methyl t-butyl ether.
10. The method according to claim 1, wherein the crystallization conditions in step (2) are: the temperature is 5-15 ℃, and the crystallization time is 12-24 hours.
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